Phenoxy-, phenylthio-and phenylamino-1, 3, 5-triazines



United States Patent 3,245,992 PHENOXY-, PHENYLTHIO- AND PHENYLAMINO-1,3,5-TRIAZINES Martin Dexter, Briarcliif Manor, Martin Knell,Ossinirig, and Eric A. Roskin, Bronx, N.Y., assignors to Gelgy ChemicalCorporation, Greenburgh, N.Y., a corporation of Delaware No Drawing.Filed July 20, 1965, Ser. No. 473,478 4 Claims. (Cl. 260248) Thisapplication is a cont-inuation-in-part of copending application SerialNo. 361,533, filed April 21, 1964, now allowed, which in turn is acontinuation-in-part of copending application Serial No. 87,520, filedFebruary 21, 1961, now abandoned, which in turn is a continuation-inpartof copend-ing application Serial No. 47,159, filed August 3, 1960, nowabandoned, which in turn is a continuation-in-part of copendingapplication Serial No. 21,- 604, filed April 12, 1960, now abandoned.

The compounds of this invention may be represented by the formula:

wherein each .of R and R is either the group and each of X, Z and Y iseither O, -S or in which each of n, m, z and y has a valueof from 0'1012, each of a and x has a value of from 0 vto 3.0, .q hasavalue of from2 to 6, p has a value of from -0 to 3, and b has a value of from 0 to 1.

R and R may be alike .or different and may be hydrogen, alkyl,alkylthio(lower)alkyl, alkylthio (lower)alkyl.- thio (lower) alkyl oralkylthio (lower) alkylthioflower) alkylthio(lower)alkyl. R and R mayalso be =pheny1, mono (lower) alkylphenyl, di (lower) alkylphenyl,hydroxyphenyl, mono(-lower) alkyl-hydIQXyphenyl ordi(lower)alkylhydroxyphenyl.

It will also be observed that in each instance the triazine compounds ofthe present invention possess ;a hydroxyphenyl group or alternatively,.in :the m re preferred species, a mono or ditlower) alkylhydroxyphenylgroup. The hydroxy group may be in the ortho, meta ice or para positions(with respect to the group joining the p e y g up to t e triazine r ng)altho gh th pa a Position is preferred. While the (lower) alkyl gIOiPS Oi this hydroxyphenyl group may be any saturated hydrocarbon having fromone to ,six carbon atoms, the t-butyl group is especially preferred.Furthermore While 9116 or two alkyl groups may be in any of theremaining four positions in the hydroxyphenyl group, it is generallydesirable, if possible, for at least one and preferably both :to be onthe carbon atoms of the phenyl ring which are adjacent to the hydroxygroup. i

X, Y and Z may be alike or different and may be a divalent oxygen atom,a divalent sulfur atom, an imino group or an alkylimino group.

By the term alky is meant a branched or straight chained saturatedhydrocarbon group of from one to about thirty carbon atoms.Representative of such groups are thus methyl, ethyl, propyl, isopropyl,butyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl,tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl,hexacosyl, ,octacosyl, triacontyl and the like. When the term alkyl isqualified by the designation (lower), there is included branched orstraight chained hydrocarbon groups of from one to about six carbonatoms; e.g., methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl,pentyl, hexyl and the like.

Compounds falling within the above formula are surprisingly effectivestabilizers of organic material normally subject to deterioration,presumably oxidative deterioration. Such material includes for example,synthetic organic polymeric substances such as vinyl resins formed bythe polymerization of vinyl halides or from the copolymerization ofvinyl halides with unsaturated polymerizable compounds, e.g., vinylesters, wit-unsaturated esters, a,/3- unsaturated acids,a,fi-unsaturated ketones or aldehydes and unsaturated hydrocarbons suchas butadiene and styrene; poly-rx-olefins such as polypropylene,polyethylene, polybuylene, polyisoprene and the like, includingcopolymers of poly-u-olefins; polyurethanes such as are prepared frompolyols and organic polyisocyanates; polyamides such aspoly(hexamethylene adipamide); polyesters such as poly(methyleneterephthalates); polycarbonates; polyacetals; polystyrene; poly(ethyleneoxide); copolymers such as those formed by the copolymerization ofacrylonitrile, butadiene and/or styrene; as well as physical mixtures ofthe above such as high impact polystyrene containing copolymers ofbutadiene and styrene; and the like.

Other materials stabilized by the present invention include lubricatingoils such as those of the aliphatic ester type, e.g., dihexyl azelate,di-(Z-ethylhexyl)azelate, di-( 3, 5,5 trimethylhexyl)glutarate,di-(3,5,5-trimethylpentyl) glutarate, di-(2-ethylhexyl)pimelate,di-(Z-ethylhexyl) adipate, diisoamyl adipate, triamyltricarballate,pentaerythritol tetracaproate, dipropylene glycol dipelargonate, 1,5-pentanediol di-(2-ethylhexanoate), and the like; fats and oils of animaland vegetable origin, e.g., linseed oil, menhaden voil, cod liver oil,castor oil, olive oil, rapeseed oil, coconut -oil, palm oil, corn oil,sesame oil, peanut oil, cotton seed oil, butter, fat, lard, beef 'tallowand the like; saturated and unsaturated hydrocarbons such as forexample, both natural and synthetic gasolines, jet fuels, diesel oils,mineral oils, fuel oils, drying oils, waxes and resins.

A particularly valuable class of organic materials stabilized by thecompounds of the present invention are those of the group consisting ofpolypropylene, polyethylene, polystyrene, aliphatic aldehydes, aliphaticester lubricants, fats, oils of animal origin, oils of vegetable origin,hydrocarbons boiling in the gasoline range, mineral oil and hydrocarbonwax.

By utilizing from about 0.001% to about 10% by weight, preferably fromabout 0.001% to about 5% by weight, of the compounds of this invention,such organic materials are stabilized during processing, e.g., millingof polypropylene, blow molding of polyethylene and during use. Suchsigns of oxidative deterioration as discolorization and embrittlement ofpolymers, gumming of hydrocarbons, spoilage of oils and fats and thelike are thus substantially eliminated, reduced and/or retarded by thepresence of a stabilizing amount of these compounds.

These compounds may be used singly, in combination with one another, orin conjunction with other additives such as antioxidants, pourpointdepressants, corrosion and rust inhibitors, dispersing agents,demulsifiers, antifoam agents, carbon black, accelerators, plasticizers,color stabilizers, heat stabilizers, ultraviolet adsorbers, dyes,pigments and the like. Not only are the functions of such additivesunimpaired, they are often improved. Furthermore in certain instances,the addition of a so-called synergist such as dilaurylthiodipropionate,or similar sulfur-containing esters, greatly increases the stabilizingproperties of these compounds. This is particularly evident withsymmetrical compounds of the present invention such as 2,4,6 tris 4(hydroxy 3,5 di t butylphenoxy)- 1,3,5-triazine which falls withinFormula V, infra.

Particularly valuable subclasses of compounds are those of FormulasII-VII below in which m and n are as defined for Formula I:

cam-H rr-(onmn) wherein R and R are each and each of X and Y is O-, S-or (C nH2n)H and wherein each of n, m, z and y has a value of from O to12, and a has a value of from 0 to 30.

The compounds of the present invention are preferably prepared fromcyanuric chloride although triazine com of X, Y and Z is oxygen, ahydroxy compound is employed to react with one or more of the chlorineatoms of the triazine ring. When one or more of X, Y and Z is sulfur, amercapt-an may be employed to react with one or more chlorine atoms onthe triazine ring. Similarly when one or more of X, Y and Z is imino, anamine is employed to react with one or more of the chlorine atoms on thetriazine ring. Other variations are of course possible, such as reactinga halide with a mono, di or trimercaptotriazine. The number of groupsintroduced on any triazine intermediate having more than one chlorineatom present may be controlled as for example by limiting the quantitiesof reactants.

The following chart demonstrates some of the various alternativesynthetic routes available, starting with cyanuric chloride (VIII) tovarious final compounds (IX- XVIII). In those instances in which two ormore like groups are introduced all may of course be introduced in onestep. In this schematic representation, R is a nonspeclfic designationembracing R R (including hydrogen) and the hydroxyphenyl group ofFormula -I. It is The following examples will further serve to typifyalso to be understood that the H of ROH and RSH and illustrate thenature of this invention but are not may be replaced by sodium,potassium or another suitable intended in any Way as a limitation of thescope thereof. halogen reactive group. In these examples, parts are byweight unless otherwise m R w R J R N m m A IN m A m N O N R m m H H L 0R DM y f R DM N R. N 1 N 1 N 7/ D N N m N N 0 N It 0 A N i s N n H R m mH m 0 0 m 0 R 0 R O R 7 R H R R R H H O H w/ R i R H R R N m m .l 1 1 Ro N R N R C R c O R m z H a H 2 H R N N P N N R N N l N D 1 N M N Nm N NN N e Nn a N i NHP NH l l i W m m m m m w m t R H H H H m N m m K R R m1 2 l R R N C R O H s .H S 1 a H R N H R N N 1 N M l N N N w N N c N 0 AN Ii N w. s R M M! M M M m m q h m R N A N m m N m IA D V m i m ROH(XIV) noted and the relationship of parts by weight to parts by volumeis as that of grams to cubic centimeters. Temperature is expressed indegrees centigrade,

EXAMPLE 1 6- (4-hydr0xy-3,5-di-t-butylanilino) -2,4- bis- (n-octyl thio)-l ,3 ,5 -triazine (a) 4 nitroso 2,6-di-t-butylphenol.-Seven hundred andfifty parts by volume of ethanol, cooled at 15, are saturated withhydrogen chloride gas and then diluted by the addition of 4000 parts byvolume of ethanol. 2,6- di-t-butylphenol (824 parts) is dissolved in thealcoholic solution and a solution of sodium nitrite (304 parts in 400parts by volume of water) is added at 1520 over a period of one hourwhile stirring. Stirring is continued for another 2 hours, allowing thetemperature to rise to room temperature. Two thousand parts by volume ofwater are then added. The product is collected by filtration and washedwell with water. The filter cake is slurried in 3000 parts by volume ofpetroleum ether, filtered, washed on the filter with 1000 parts byvolume of petroleum ether and dried in a vacuum oven at 70-80 to yield4-nitroso-2,6-di-t-butylphenol, M.P. 219.

(b) Lamina-2,6 di-t butylphenol.4-nitroso-2,6-dit-butylphenol (176parts) is dissolved in 600 parts by volume of 5 N sodium hydroxide and1200 parts by volume of water and a solution of sodium hydrosulfite (522parts) in 2200 parts by volume of water is added with moderate speed(about 30 minutes), during which time the temperature rises to about 53.After addition is complete, stirring is continued for 2% hours. Theprodnot is rapidly collected by filtration, washed with 4000 parts byvolume of water and dried in a vacuum desiccator over phosphoricanhydride to yield 4-amin0-2,6-dit-butylphenol, M.P. IDS-108.

(c) 6-(4-hydroxy-3,5 di-t-butylanilino)-2,4-dichlro- 1,3,5-triazine.Asolution of cyanuric chloride (18.4 parts) in boiling acetone (100 partsby volume) is poured in a thin stream into 200 parts by volume ofice-water with stirring, maintaining the temperature of 0 with externalcooling. 4-amino-2,6-di-t-butylphenol (22.1 parts) and 5.3 parts ofsodium carbonate are then added and the reaction mixture stirredvigorously at 8-10" for 45 minutes. This mixture is then diluted by theaddition of 100 parts (by volume of acetone, with stirring continued foran addition-a1 hour at 8-10". The suspension is then poured into 500parts by volume of ice-water and the precipitate is filtered 01f anddried in vacuo to yield 6-(4 hydroxy-3,S-di-t-butylanilino) 2,4dichloro-l,3,5- triazine, M.P. 144".

(d) 6-(4 hydr0xy-3,5-di-t-butylalzilino) 2,4bis-(noctylthio)-1,3,5-triazine.An alcoholic solution of sodiumn-octylmercaptide (prepared by dissolving 2.3 parts of sodium in 50parts by volume of ethanol and addition 14.6 parts of n-octylmercaptan)is added rapidly with stirring to a solution of 18.5 parts of6-(4-hydroxy-3,S- di-tb-utylanilino)-2,4-dichloro-1,3,5-triazine in 150parts by volume of ethanol. The reaction mixture is stirred at refluxfor 1% hours. After cooling to normal room temperature, 500 parts byvolume of water are added. The precipitated product is separated byfiltration and washed well with water. Purification of the product isaccomplished by dissolving in 300 parts by volume of boiling ethanol,adding activated carbon, filtering and slowly recrystallizing. The whiteneedles which form are collected by filtration, washed with cold ethanoland dried in vacuo to yield 6-(4 hydroxy-3,S-di-t-butylanilino)-2,4-bis-(n-octylthio)-1,3,5-triazine, M.P. 92-95. Additional material havingthe same melting point may be obtained by concentration of the motherliquor.

By replacing n-octylmercaptan by ethylmercaptan, noctadecylrnercaptan,t-butylmercaptan and pt-butylthiophenol respectively, the followingcompounds are obtained:

6-(4-hydroxy-3,S-di-t-butylanilino) 2,4-bis-(ethylthio)- 1,3,5-triazine,M.P. 8990 (recryst. from petroleum ether)6-(4-hydroxy-3,S-di-t-butylanilino) 2,4-bis-(n-ootadecy1-thio)-1,3,5-triazine, M.P. 8688 (recryst. from ethanol and petroleumether) 6- (4-hydroxy-3,S-di-t-butylanilino) 2,4bis-(t-butylthio)-1,3,5-triazine, M.P. l69-l70 (recryst. from benzene and heptane)6-(4-hydroxy-3,5 di-t-butylanilino)2,4-bis-(p-t-butylphenylthio)-1,3,5-triazine, M.P. 87.

EXAMPLE 2 4,6-bis- 4 -hydroxy-3,5 -di-t-buty Ian il ino)2-n-0ctylthi0-1,3,5-triazine (a) 4,6 bis; (4 hydroxy 3,5di-t-butyIanilin0)-2- chloro-J,3,5-triazin'e.-A solution of 4.6 parts ofcyanuric chloride in parts by volume of boiling acetone is poured in athin stream into 200 parts by volume of icewater While stirring,maintaining a temperature of 0-5 by means of external cooling.4-amino-2,6-di-t-butyl phenol (16.7 parts) and 6.3 parts of sodiumbicarbonate are then added with vigorous stirring, the temperature beingmaintained at 10 for 45 minutes. The temperature is raised to 50 andheld there for 45 minutes, and then to reflux for 45 minutes. The brownsolid which precipitates is filtered off, washed well with water andpetroleum ether and is finally recrystallized from dioxanehexane (5:4)to yield4,6-bis-(4-hydroxy-3,S-di-t-butylanilino)-2-chloro-1,3,5-triazine, M.P.304 (dec.).

(b) 4,6-bis-(4 hydr0xy-3,5-di-t-butylanilino)-2-acrylthio-l,3,5-triazine.-An alcoholic solution of sodiumnoctylmercaptide (prepared by dissolving 0.172 parts of sodium in 10parts by volume of ethanol and adding 1.09 parts of n-octylmercaptan)added to a suspension of 4.15 parts of2,4-bis-(4-hydroxy-3,S-di-t-butylanilino)- 6-chloro-1,3,5-triazine inparts by volume of ethanol and this mixture then refluxed for 1 hour.The alcoholic solution is filtered hot to remove 1.2 parts of insolublematerial and then flooded with 500 parts by volume of water. The solidmaterial which forms is collected by filtration, washed with diluteaqueous sodium hydroxide and water and finally dried in vacuo to yield4,6-bis-(4- hydroxy-3,5di-t-butylanilino)-2 octylthio 1,3,5-tr-iazine,M.P. 55.

By alternatively employing sodium p-octadecylphenyl mercaptide, there isobtained according to this procedure, 4,6 bis (4 hydroxy 3,5 di tbutylanilino) 2 poctadecylphenylthio-l|,3,5-triazine.

EXAMPLE 3 6- (4-hydr0xy-3,5-di-t-b utylam'lina) -2,4-bis- (phenylthio)-1,3,5-triazine A mixture of 11.1 parts of6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine, 6.6parts of thiophenol and 4.74 parts of pyridine in 100 parts by volume ofacetone is stirred at normal room temperature for 30 minutes, afterwhich the reaction mixture is stirred at reflux for 1% hours. Afterbeing cooled to normal room temperature, the pyridine hydrochloridewhich forms is removed by filtration and the filtrate flooded withwater, causing the formation of a gummy precipitate. The supernatantliquid is decanted and the resulting viscous mass is boiled in ethanol(100 parts by volume). The yellow crystals which form upon cooling arecollected by filtration, washed with ethanol and dried in vacuo, toyield 6 (4 hydroxy 3,5 di t butylanilino) 2,4 bis-(phenylthio)-1,3,5triazine, M.P. 169-170". Additional material may beobtained by chilling the mother liquor.

In a similar fashion, 12.8 parts of 6-(4-hydroxyanilino)-2,4-dichloro-1,3,5-triazine are allowed to react with a solution of 11parts t thiophenol, in 150 parts by volume of acetone and 7.9 parts ofpyridine in 25 parts by volume of acetone. After flooding with water,the gummy precipitate solidifies upon trituration with water andstanding. This solid is purified by redissolving in base andsubsequently treating with activated carbon. The purified solution,after filtration, is neutralized with dilute hydrogen chloride, and theprecipitate collected and dried to yield6-(4-hydroxyanilino)-2,4-bis-(phenolthio)-1,3,5- triazine, M.P. 72-78".

The starting compound 6-(4-hydroxyanilino)-2,4-dichloro-1\,3,5-triazineis prepared by reacting cyanuric chloride with 4-aminophenol in a manneranalogous to the preparation described in Example 1(c).

EXAMPLE 4 6- (4-hydr0xy-3,5-di-t-butylanilino -2,4-bis- (anilino)-1,3,5-triazine A cold (5) solution of 14.75 parts of 6-(4-hydroxy-3,5-di-t-butylanilino-2,4-dichloro-1,3,5-triazine and 7.6 parts ofaniline in 100 parts by volume of acetone is allowed to slowly attain atemperature of while maintaining a pH of between 7 and 8 by the additionof 5 N sodium hydroxide. When the pH is constant, 200 parts by volume ofwater are added and the reaction mixture is heated to boiling, allowingthe acetone to distill off, the pH being kept between 7 and 8 byaddition of 5 N sodium hydroxide. After the theoretical amount of alkalihas been added and the pH remains at 7, the mixture is heated at refluxfor an additional minutes. The solid obtained is collected by filtrationof the hot suspension, washed well with water, air dried and finallytriturated with hexane and redried to yield6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-(anilino)1,3,5-triazine as awhite solid, M.P. 192-194. Further purification may be accomplished byrecrystallization from isopropyl alcohol.

EXAMPLE 5 6- (4-lzydr0xy-3,5-di-t-butylanilino)-2,4-bis- (n-octylamino)-1,3,5-lriazine n-Octylamine (12.9 parts), 18.5 parts of 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine and 5.3 parts ofsodium carbonate are added to 200 parts by volume of water. The mixtureis heated at reflux for /2 hour and methyl Cellosolve (200 parts byvolume) is then added with reflux being continued for an additional 6hours. Three hundred parts by volume of water are then added. Uponstanding, an oily layer separates and becomes a thick resinous mass. Onehundred parts by volume of 5 N hydrochloric acid are added and theproduct extracted with ether. The resultant ethereal solution is washedwith water, dilute sodium hydroxide and again with water and then driedover anhydrous sodium sulfate, filtered, and evaporated to yield6-(4-hydroxy-3,5- di t butylanilino) 2,4 bis (n octylamino) 1,3,5-triazine, M.P. 4245.

EXAMPLE 6 6- (4-hydr0xy-3,S-di-t-butylanilino -2,4-bis- (phenoxy,3,5-triazine A solution of 7.36 parts of 6-(4hydroxy-3,5-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine in parts byvolume of ethanol is added to a stirred alcoholic solution of sodiumphenoxide (prepared by dissolving 0.92 part of sodium in 25 parts byvolume of ethanol and adding 3.76 parts of phenol). After the exothermicreaction has subsided, the reaction mixture is heated at reflux for 2hours. The sodium chloride is removed by filtration and the filtrateflooded with water to produce a gummy yellow solid which, on triturationwith petroleum ether, yields a white solid. This is recrystallized frommethanol-water (5:1) to yield6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-bis- (phenoxy)-1,3,5-triazine,M.P. 160-l61|.

10 EXAMPLE 7 6 (4 hydroxy 3,5-di-t-butylanilin 0)-2,4-bis-(eth0xy)-1,3,5-triazine A solution of 10 parts of6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine in 25parts by volume of ethanol is added rapidly with stirring to a solutionof 1.24 parts of sodium in 50 parts by volume of ethanol. The reactionmixture is stirred at reflux for 1 hour after which, the sodium chloridewhich forms is removed by filtration. The filtrate is purified withactive carbon, filtered and flooded with water. The oil which forms isseparated and extracted with ether and these extracts are dried overanhydrous magnesium sulfate and evaporated. When the last traces ofsolvent are removed under high vacuum, the residue solidifies to yield6-(4-hydroxy-3,5-dit-buty1anilino)-2,4-bis-(ethoxy)-1,3,5-triazine, M.P.54.

EXAMPLE 8 6 (4 hydroxy 3,5 di-t-butylanilino)-2,4-bis-(n-0clyloxy-1,3,5-lriazine Ten parts of 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine are added to a solution of 1.24 parts of sodium in50 parts by volume of n-octyl alcohol while stirring. An exothermicreaction ensues and the temperature is not allowed to rise above 60.Stirring is continuedat 60 for 15 minutes and the excess octyl alcoholis then removed by distillation under high vacuum with a maximum bathtemperature of The product obtained as a resinous oil is purified bydissolution in hexane and by placing the solution on a silica gelcolumn, eluting first with hexane-benzene (1:1) and then with benzene. 6(4 hydroxy 3,5 di-t-butylanilino)-2,4-bis-(n-octy1- oxy)-1,3,5-triazine,a resinous oil, is isolated by evaporation of the benzene eluate.

Calc. for C H O N C, 71.19; H, 10.14; N, 10.05. Found: C, 71.13; H,10.12; N, 10.07.

EXAMPLE 9 6 (2 hydroxy 3 t-butyl-S-methylanilino)-2,4-biS-(noctylthz'o)-1,3,5-triazine (a) 2,4 bis (n octylthio )-6-chl0r0-],3,5-lriazine. Asolution of 36.8 parts of cyanuric chloride, 58.4 parts ofn-octylmercaptan and 0.3 part by volume of pyridine in parts by volumeof xylene is refluxed for 6 hours, with nitrogen being passed throughthe reactants, until the evolution of hydrogen chloride has ceased. Thesolution is separated by filtration from a small amount of insolublematerial, the solvent removed under vacuum, and the residue then vacuumdistilled to yield 2,4-bis- (n-octylthio)-6-chloro-1,3,5-triazine, B.P.206-208/0.075 mm.

(b) 6 (2 hydroxy 3 t-butyl-S-methylanilino)-2,4-bis-(n-oclyllhz'o)-],3,5-triazine.-A mixture of 10.1 parts of6-c.hloro-2,4-bis-(n-octylthio)-l,3,5-triazine, 4.7 parts of2-amino-4-methyl-6-t-butylphenol and 100 parts by volume of water isgradually warmed with stirring under a nitrogen atmosphere to 70,maintaining the pH at 7-8 by the addition of 5 N aqueous sodiumhydroxide. When the pH remains constant, the oily layer is extractedwith ether and these extracts dried over anhydrous magnesium sulfate.The magnesium sulfate is removed by filtration and the filtrateevaporated. The residue is purified by dis solving in petroleum ether,placing the solution on a silica gel chromatographic column, and elutingwith benzene. After removal of the benzene, 6-(2-hydroxy-3-t-butyl-5-methylanilino) 2,4-bis-(n-octylthio)-1,3,5-triazine is obtained as aresinous oil.

Calc. for C H N S O: C, 65.91; H, 9.22; N, 10.24. Found: C, 66.06; H,9.24; N, 10.45.

In a similar manner, 6 (4 hydroxy3,5-di-isopropylanilino)-2,4-bis-(n-octylthio)-1,3,5-triazine isprepared by substituting 4-amino-2,6-di-isopropylphenol [prepared by themethod described for the preparation of 4-amino-2,6-

1 1 di-t-butylphenol in Example 1(a) through (b)] for the 2-amino-4-methyl-6-t-butylphenol. This product is also obtained as aresinous oil.

Calc. for C H N S C, 66.37; H, 9.35; N, 9.99. Found: C, 66.06; H, 9.17;N, 10.27.

In a similar fashion,6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis-(n-octylthio)-1,3,5-triazineis prepared by substituting 4-amino-2-methyl-6-t-butylphenol [preparedby the method described for the preparation of 4-amino-2,6-di-t-butylphenol in Example 1(a) through (b)] for the2-amino-4-methyl-G-t-butylphenol. This product is also obtained as aresinous oil.

Calc. for C H N S O: C, 65.91; H, 9.22; N, 10.24. Found: C, 66.07; H,8.87; N, 10.40.

Likewise, 6 (4 hydroxyanilino)-2,4-bis-(n-octylthio)- 1,3,5-triazine isprepared by substituting p-aminophenol for the2-amino-4-methyl-G-t-butylphenol. The product is a solid and in place ofchromatography, the product is recrystallized from petroleum ether, M.P.6263.

In a similar manner, 6 (4 hydroxy-3,S-di-methylanilino) 2,4 bis (noctylthio)-l,3,5-triazine is prepared by substituting4-amino-2,6-dimethylphenol [prepared by nitrosation of2,6-dimethylphenol as in Example 1(a) and catalytic reduction usingpalladium on carbon catalyst] for the 2-amino-4-methyl-6-t-butylphenol.The product is a solid and in place of chromatography, the product isrecrystallized twice from petroleum ether, M.P. 70-71.

EXAMPLE 10 6- (4-hydr0xy-3,5-di-t-butylanilino)-2,4-bis-(n-octylthioethyllhio -J ,3 ,S-triazine An alcoholic solution of sodiumn-octylthioethylmercaptide prepared by dissolving 0.92 parts of sodiumin parts by volume of ethanol and adding 8.58 parts ofn-octylthioethylmercaptan [prepared according to the method described byReid, Organic Chemistry of Bivalent Sulphur, Chemical Publishing C0.,New York, N.Y., 1958, p. 394] is added With stirring to a slurry of 7.38arts of 6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-dichloro- 1,3,5-triazinein 20 parts by volume of ethanol. After the exothermic reaction hassubsided, the reaction mixture is heated at steam bath temperature for 1hour, cooled to room temperature and filtered. Upon standing overnight,the product crystallizes from the filtrate to yield 6- (4-hydroxy-3 ,5-di-t-butylanilino -2,4-bis- (n-octylthioethylthio)-1,3,5-triazine,which after recrystallization from hexane, is a waxy solid, M.P. 69-71.Additional material is obtained by careful addition of Water to themother liquor until crystallization occurs.

EXAMPLE 11 6- (4-hya'roxy-3,S-di-t-butylanilino) -2,4-bis- (4-l-l2utylplzerzoxy -1 ,3 ,5 -trz'azine' An alcoholic solution of sodiump,t-butylphenoxide (prepared by dissolving 9.2 parts of sodium in 750parts by volume of ethanol and adding 60 parts of p,t-butylphenol) isadded rapidly with stirring to a slurry of 74 parts of6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-dichloro- 1,3,5-triazine in 250parts of ethanol. After the exothermic reaction subsides, the reactionis allowed to stand for several hours and then poured into 2000 parts ofwater. The gummy solid is separated by filtration and recrystallizedfrom methanol-water (100:7) to yield 6-(4- hydroxy 3,5 di tbutylanilino) 2,4 bis (4 tbutylphenoxy)-l,3,5-triazine, M.P. 11912l.

By replacing p,t-butylphenol by p,t-octylphenol in this procedure, thereis obtained 6-(4-hydroxy-3,S-di-t-butylanilino) 2,4 bis (4 toctylphenoxy) 1,3,5 triazine, M.P. 99-101 (recrystallized frommethanol).

If sodium p-octadecylphenolate is substituted for sodiump,t-butylphenoxidc in this example, there is obtained 6 (4 hydroxy 3,5di t butylanilino) 2,4 bis- (p-octadecylphenoxy)-1,3,5-triazine.

If sodium methylmercaptide is substituted for sodium p,t-butylphenolatein this example, there is obtained 6-(4- hydroxy 3,5 di t butylanilino)2,4 bis (methylthio) -1,3 ,5 -triazine.

EXAMPLE 12 6- (4-hydr0xy-5-methylanilino) -2,4-bis- (n-octylthio) ,3 ,5-trz'azine A mixture of 10.1 parts of 2,4-bis-(n-octylthio)-6-chloro-1,3,5-triazine, 3.08 parts of 2-rnethy1-4-aminophenol and 100parts of water is gradually warmed with stirring under a nitrogenatmosphere to 90, the pH being maintained at 6-7 by the addition of 5 Nsodium hydroxide. When the pH is constant, the reaction is complete. Theproduct is collected by filtration, washed with Water and purified byrecrystallization from hexane to yield 6 (4 hydroxy 5 methylanilino) 2,4bis (noctylthio)-1,3,5-triazine, M.P. 6768.

In place of 2-methyl-4-aminophenol the following compounds are employedin equivalent amounts: 2- amino-4-methylphenol, m-aminophenol,p-methylamin0- phenol sulfate, o-arninophenol, 2-tbutyl-4-aminophenol,3,5-dimethyl-4-aminophenol, 2-amino-4,6-di-t-butylphenol and2-amino-4-t-butylphenol. The following compounds are thus respectivelyobtained:

6-(2-hydroxy-S-methylanilino)-2,4-bis-(n-octylthio)- 1,3,5-triazine,M.P. 99-l01 (recryst. from ethanol and heptane);

6-(3-hydroxyanilino) -2,4-bis-(n-octylthio)-1,3,5-

triazine, M.P. 5557 (recryst. from petroleum ether);

6-(4-hydroxy-N-rnethylanilino -2,4-bis- (n-octylthio 1,3,5-triazine,M.P. 5557 (recryst. from hexane, heptane and petroleum ether);

6-(Z-hydroxyanilino).-2,4-bis-(n-octylthio) 1,3,5-

triazine, M.P. 103 (recryst. from benzene-hexane and methanol-water)6-(4-hydroxy-5-t-butylanilino) -2,4-bis- (n-octylthio)-1,3,5- triazine,M.P. (isolated by elution chromatography using a silica gel column, thenrecryst. from petroleum ether) 6- (4hydroxy-2,6-dimethylanilino-2,4-bisn-octylthio) 1,3,5-triazine, M.P. 122-123 (recryst. fromheptane);

6-(2-hydroxy-3,S-di-t-butylanilino)-2,4-bis-(n-octylthio)- 1,3,S-triazine, M.P. 74 (recryst. from ethanol-Water and methanol) and 6-2-hydroxy-S-t-butylaninlino -2,4-bis- -octylthio) 1,3,5-triazine, M.P.101 (recryst. from methanol).

If 3-octadecyl-4-arninophenol is substituted for 2- methyl-4-aminophenolin this example, there is obtained 6 (4 hydroxy 2 octadecylanilino) 2,4bis (noctylthio)-1,3,5-triazine.

EXAMPLE 13 6- (4-hydr0xy-3,5-di-t-butylphenylthio)-2,4-bis(n-0ctylthi0)-1,3,5-triazine An alcoholic solution of sodium 4-hydroxy-3,5-di-tbutylphenylmercaptide (prepared by dissolving 23 partsof sodium in 2000 parts by volume of ethanol and adding 238 parts of4-mercapto-2,6di-t-butylphenol [Hotelling et al., J. Org. Chem. 24, 1958(1959)]) is added with stinring to .a solution of 404 parts of2,4-bis-(n-octylthio)- 6-ohloro-l,3,5-triazine in 2000 parts by volumeof ethanol. After the exothermic reaction has subsided, the reaction isallowed to stand at normal room temperature for several hours. The solidis removed by filtration and the ethanol removed from the filtrate byevaporation. The oily residue is then dissolved in hexane and adsorbedon a silica gel column. After removing impurities by elution withhexane, the product,6-(4-hydroxy-3,5-di-t-butylphenylthio)-2,4bis-(n-octylthio)-=1,3,5-t1riazineis eluted with 50% by volume of benzene-hexane and isolated byevaporation of the solvent.

Calc. for C H ON S C, 65.4; H, 9.15; N, 6.93; S, 15.88. Found: C, 65.29;H, 9.15; N, 6.73; S, 16.16.

By replacing 4-mercapto-2,G-di-t-butylphenol with 4-rnercapto-Z,6-dimethylphenol [Hotelling et al., J. Org. Chem. 24, 1958(1959)], 6-(4ahydroxy-3,5-dimethylphenylthio)-2,5-bis(-n-octylthio)-1,3,5-triazine is obtained (isolated by elutionchromatography using a silica gel column and eluting with 75% by volumebe-nzene hexane).

Calc. for C27H43ON3S3I C, 62.15; H, 8.31; N, 8.05; S, 18.44. Found: C,62.13; H, 7.93; N, 7.63; S, 18.37.

In an analogous fashion,6-(4-hydroXy-3,5-di-t-butylanilino)-2,4-bis-(2,3-d-imethylphenylthio)-1,3,5triazine is obtained which when 7.4 parts of6-(4-hydroxy-3,5-di-tbutylanilino)-2,4-dic-hloro-1,3,5-triazine in 100parts by volume of ethanol are mixed with 8.4 parts of 2,3-dimeth-.ylbenzenet hiol (66% pure oil) and 0.92 part of sodium dissolved in 50parts by volume of ethanol. The result ant mixture is allowed to standfor 2 hours, after which the salt which forms is removed by filtrationand the filtnate treated with steam to remove volatiles, includingethanol. The residual oil solidifies and the aqueous layer is decanted.This solid is dissolved in petroleum ether and the resultant mixturedried over magnesium sulfate. Upon evaporation of the petroleum ether,6-(4-hydroxy- 3,-5-di t-butylanilino)-2,4-bis-(2,3-dirnethylphenylthio)1, 3,5-triazine is obtained, and further purified by dissolution inhexane and chromatography on a silica gel column using 50%benzene-hexane as the eluant.

. Calc. for C H N SO C, 69.2; H, 7.04; N, 9.78; S, 11.19. Found: C,69.52; H, 7.6; N, 9.65; S, 11.62.

EXAMPLE 14 6 4 -hydrxy-3 ,5 -di-t-buty lphenoxy -2,4 bis- (n-octylthio)-1,3,5-triazine An alcoholic solution of sodium4-hydroxy-3,5-di-tbutylphenoxide, prepared by dissolving 60 parts ofsodium in 5000 parts by volume of ethanol and adding 666 parts of2,6-d-i-t-butylhydroquinone, is added rapidly to a stirred solution of1212 parts of 2,4-bis-(n-octylthio)-6chlor0-1, 3,5-triazine in 2500parts by volume of ethanol. After the exothermic reaction subsides, thereaction mixture is allowed to stand several hours and the solid thenremoved by filtration. The filtrate is clarified with activated carbon,filtered and concentrated to dryness under vacuum. The oily residue thusobtained is dissolved in hexane, adsorbed on a silica gel column andeluted with 50% benzene hexane to yield6-(4-hydroxy-3,5-di-t-butylphenoxy)- 2,4-bis-(n-octylthio)1,3,5-triazineas alight colored viscous oil.

Calc. for C H O N S C, 67.19; H, 9.4; N, 7.12. Found: C, 66.84; H, 9.11;N, 7.26.

By replacing the 2,6-di-t-butylhydroquinone with hydroquinone, thechromatographic separation is unnecessary, the crude reaction productbeing precipitated by the addition of water. Fractional crystallizationfrom ethanol separates two products, the latter of which is 6-(4-hydroxyphenoxy)-2,4-bis-(n-octylthio) 1,3,5 triazine, M.P. 79-80".

Similarly by employing 2-t-butyl-6-methylhyd1roquinone andZ-methylhy-droquinone in the foregoing procedure, there are respectivelyobtained 6-(4 hydroxy-3-methyl-5-tbutylphenoxy)2,4-bis-(n-octylthio)-l,3,5-triazine, M.P. 61-63", and6-(4-hydroXy-3-methylp:henoxy) -2,4-bis- (noctylthio) 1,3,5-tri-azine,M.P. 5659.

Compounds of the type herein exemplified can also be advantageouslyprepared by first treating cyanuric chloride with one equivalent of theappropriate hydroquinone or derivative thereof and thereafterintroducing two equivalents of the appropriate mercaptan.

EXAMPLE 15 (a) 2,4-dich'loro-o-moctylthi0-J,3,5-triazine.- A solution of184.4 parts of cyanuric chloride, 146 parts of noctylmercaptan and 0.5part by volume of pyridine in 500 parts by volume of xylene is refluxedwhile passing nitrogen through the reactants until the evolution ofhydrogen chloride has ceased. The solution is then filtered from a smallamount of insoluble material and the solvent removed under vacuum.Vacuum distillation of the residue yields2,4-di-chloro-6-(n-octylthio)-1,3,5 triazine, B.P. 147148/0.050 mm.

(b) 2,4-l2is-( l-hydroxy-3,5-di-l-butylphn0xy)-6(noctylthz'o)-],3,5-triazine.-To a vigorouslyv stirred solution of 8.82parts of 2,4-dichloro-6-(n-octylthio)-1,3,5- triazine and 13.32 parts of2,6-di-t-butyl- 1,4-hydroquinone in 50 parts by volume of ethanol isadded dropwise a solution of 1.38 parts of sodium in 100 parts by volumeof ethanol over a period of 30 minutes. The reaction mixture is refluxedfor an additional 30 minutes, cooled and filtered. The filtrate isreheated to boiling and 20 parts by volume of water are added. Uponcooling the product which crystallizes is collected by filtration anddried to yield 2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine, M.P. 129-134. Recrystallization fromethanol-water raises the melting point to 133134.

If 5.88 parts of 2,4-dichloro-6-(n-octylthio)-l,3,5-triazine are reactedwith 6.64 parts of mono-t-butyl-1,4-hydroquinone in an analogous mannerto the preparation described in this example, then2,4-bis-(4-hydroxy-3-t-butylphenoxy)-6-n-octylthio-1,3,5-triazine 'isproduced. This product is isolated by elution chromatography on a silicagel column using benzene as eluant. Upon evaporation of the solvent, theproduct is obtained as a hard glass.

Cale. for C H O N S: C, 67.25; H, 7.83; N, 7.59. Found: C, 67.01; H,7.82; N, 7.95.

Similarly by employing two molar equivalents of 2-methyl-6-t-butylhydroquinone in place of 2,6-di-t-butylhydroquinone,there is obtained 2,4-bis-(4-hydroxy-3- methyl-S-t-butylphenoxy)-6-(nocty-lthio) 1,3,5 triazine, M.P. 147.5-149.

2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6 (ndodecylthio)-1,3,5-triazine may be prepared according to the followingprocedure. To a stirred solution at 5 to 8 of 18.4 parts of cyanuricchloride and 20.2 :parts of ndodecylmercaptan in 100 parts by volume ofacetone under nitrogen are added dropwise 8 parts of 50% sodiumhydroxide over a 15 minute period. There is then added 45.8 parts of 97%2,6-di-t-butylhydroquinone and the resulting mixture stirred at 10 whileadding 16 parts of 50% sodium hydroxide in a dropwise fashion over 30minutes. The mixture is stirred an additional hour and the pH adjustedto 5.5 with concentrated hydrochloric acid. The solvent is removed underreduced pressure and the residue dissolved in 200 parts by volume ofboiling isopropyl alcohol. After filtering, 15 parts of water are added.The product, which crystallized slowly, is collected by filtration,washed with isopropyl alcohol, air dried and sequentially recrystallizedfrom isopropyl alcohol/Water, petroleum ether and isopropylalcohol/water. A melting point of 98 initially drops to 5558 upon afurther recrystallization from hexane but upon standing two weeks risesto 9798.

In a similar fashion by using n-butylmercaptan and employing methanol inplace of isopropyl alcohol as the isolation solvent, there is obtained2,4-bis-(4-hydroxy-3,5 di-t-butylphenoxy)-6-(n-butylthio)-1,3,5triazine, M.P. 189-191 By utilizing n-octadecylmercaptan, there isobtained 2, 4-'bis-(4-hydroXy-3,S-di-t-butylphenoxy)-6-(no'ctadecylthio)-1,3,5-triazine, M.P. 63-64". When the temperature israised very slowly, a melting point of 82 is observed.

The above compounds may also be advantageously prepared by initiallyintroducing two moles of the appropriate hydroquinone and thenintroducing one mole of the appropriate mercaptan.

1 EXAMPLE 16 6-(4-hydr0xy-3,5-di-t-butylanilino)2-(n-0'ctylthi0)-4penylthi0-1,3,5-triazine (a)6-(4-hydr0xy-3,5-di-t-butyIanilino) 4 (noctyllhio)-2-chl0r0-1,3,5-triazine.-An alcoholic solution of sodiumn-octylmercaptide, prepared by dissolving 0.23 parts of sodium in partsby volume of ethanol and adding 1.46 parts of n-octylmereaptan, is addedrapidly to a slurry of 3.69 parts of6-(4-hydroxy-3,S-di-t-butylanilino)- 2,4-dichloro-1,3,5-triazine in 10parts by volume of ethanol. The immediate exothermic reaction iscontrolled with external cooling and the reaction mixture is then pouredinto 50 parts by volume of water. The oil which separates solidifiesupon cooling and 6-(4-hydroxy-3,5-di-t-butylanilino)-4-(n-octylthio-2-chloro-1,3,5 triazine thusobtained, is collected by filtration, washed with water until free ofchloride ion, and recrystallized twice from hexane, M.P. 119129.

(b) 6-(4-hydr0xy-3,5dit-butylanilino) 2 (noctyltlzio)-4-plzenylthio-1,3,5-triazine.-To a solution of 6.55 parts of6 (4hydroxy-3,S-di-t-butylanilino)-4-(n-octylthio)-2-chloro-1,3,5-triazinein 50 parts by volume of warm ethanol is added sodium phenylmercaptide,prepared from 1.65 parts of thiophenol dissolved in a previouslyprepared solution of 0.32 part of sodium metal in 120 parts by volume ofethanol. The reaction mixture is allowed to stand for 2 hours at whichtime the pH is 7.0. The salt is removed by filtration and the ethanolsolution is treated with steam and extracted with ether. The driedethereal extracts are concentrated under reduced pressure and the yellowresin resulting is recrystallized from isopropanol/water to yieldcrystalline 6-(4-hydroxy 3,5-di-t-butylanilino)-2-(octylthio)-4phenylthio 1,3,5- triazine, M.P. 99-101".

Similarly 9.58 parts of6-(4-hydroxy-3,S-di-t-butylanilino)-4-(n-octylthio)-2-chloro 1,3,5-triazine are allowed to react with 4.44 parts of2,6-di-t-butyl-1,4-hydroquinone to yield6-(4-hydroxy-3,S-di-t-butylanilino)-4 (4-hydroxy-3,S-di-t-butylphenoxy)2 (n octylthio)- 1,3,5-triazine, which is recrystallized from n-heptane,M.P. 182183.

EXAMPLE 17 6- (4-hydr0xy-3,5-di-t-butylphenoxy 2,4-bis- (phenoxy-1,3,5-triazine Six parts of 2,4-bis-(phenoxy)-6-chloro-1,3,5-triazinedissolved in ethanol are allowed to react with a solution of 4.4 partsof 2-6-di-t-butyl-1,4-hydroquinone in sodium ethoxide which ispreviously prepared by dissolving sodium metal (0.46 part) in 30 partsby volume of ethanol. After removal of the sodium chloride formed, thefiltrate is flooded with water and the resulting solid is washed withwater, collected by filtration, dried and recrystallized from hexane toyield 6-(4-hydroxy-3,5-di-tbutylphenoxy)-2,4-bis-(phenoxy) 1,3,5triazine, M.P. 145-147".

EXAMPLE 18 2,4,6-tris-(4-hydr0xy-3,5- d i-t-butylphenoxy ,3 ,5-triazz'ne To a solution of 3.68 parts of cyanuric chloride dissolved in50 parts by volume of acetone cooled to 20 are added 13.3 parts of2,6-di-t-butyl-1,4-hydroquinone. The resultant mixture is stirred for 1hour at 20, during which time 12 parts of 5 N sodium hydroxide in 50parts of water are added dropwise. The reaction mixture is then heatedfor 30 minutes at 60 and 50 parts of water are added. The reactionmixture is heated for an additional hour at 70 until a pH of 7.0 isobtained. After cooling, the solid which forms is collected byfiltration, repeatedly washed with water, recrystallized from boilingdioxane and water and dried under reduced pressure at 125 to yield2,4,6-tris-(4-hydroxy-3,5 di-t-butylphenoxy)- 1,3,5-triazine, M.P.298-299".

EXAMPLE 19 6-(4-hydroxy-3,5-di-t-butylphenoxy)-2,4-bis-(n-octylthioethylthio)-1,3,5-triazine (a)6-(4-hydr0xy-3,5-di-t-butylphenoxy)-2,4-dichl0r0 1,3,5-triazine.To astirred solution of 18.4 parts of cyanuric chloride dissolved in 250parts by volume of acetone cooled to 5 are added 22.2 parts of2,6-di-tbutyl-1,4-hydroquinone. Twenty parts by volume of 5 N sodiumhydroxide in 250 parts by volume of water are then added dropwise withstirring over a period of 30 minutes at 5 and stirring is continued fora further 30 minutes at 5. Two hundred and fifty parts by volume .ofwater are next added and the reaction mixture stirred at 5 for 3 hours.The solid precipitate which forms is filtered, washed with ice-water anddried in vacuo to yield the intermediate 6 (4 4 hydroxy 3,5di-t-butylphenoxy)-2,4-dichloro-1,3,5-triazine, which can berecrystallized from warm isopropanol to yield crystalline material, M.P.l03-104.

(b) 6-(4-hydr0xy-3,S-di-t-butylphenoxy)-2,4bis-(noctylthioethylthio)-1,3,5-triaZine. T0 a solution of 1.38 parts ofsodium metal in 75 parts by volume of ethanol are added 13.0 parts ofn-octylthioethylmercaptan. This solution is rapidly added to a stirredsolution of 12.6 parts of crude6-(4-hydroxy-3,S-di-t-butylphenoxy)-2,4-(dichloro)-1,3,5-tr-iazine in 75parts by volume of ethanol. The initial reaction is exothermic, and thereaction mixture is heated and stirred under nitrogen for 15 minutesuntil the pH is 7.0. The reaction mixture is then treated with steam andthe resulting yellow oil extracted into parts by volume of hexane. Thesehexane extracts, after drying over magnesium sulfate, are adsorbed on asilica gel column and the product, 6-(4-hydroxy-3,5-di-t-butylphenoxy)-2,4-bis-(n-octylthioethylthio)-1,3,5-triazine, is eluted with 50%benzene in hexane and isolated as a resinous oil by evaporation.

Calc. for C H O S N C, 62.56; H, 8.94; N, 5.92; S, 18.06. Found: C,62.30; H, 8.65; N, 5.89; S, 18.37.

In a similar fashion by employing 2-t-butylhydroquinone, there isobtained 6-(4-hydroxy-B-t-butylphenoxy)2,4-bis-(n-octylthioethylthio)-1,3,5-triazine as a water insoluble oilwhich gives the following analysis:

Calc. for C H O N S S, 19.61. Found: S, 19.75, 19.46.

Alternatively, the above compounds can advantage ously be prepared bytreating one mole of cyanuric chloride with two moles of the appropriatemercaptan in the presence of base and then treating the resultant2,4-di- (alkylthiolower) alkylthio -6-chlorol ,3,5-triazine with onemole of the appropriate hydroquinone.

EXAMPLE 20 6- (4-hydr0xy-3,S-di-t-butylphenoxy -2,4-bis-(l1-dodecylthioethylthio) -1,3,5-triazine (a) n-Dodecylthioelhylmercaptan.-Asolution of 88.8 parts of n-dodecylmercaptan and 23.7 parts of sodiummethylate in 135 parts by volume of ethanol is stirred under nitrogenwhile 35.4 parts of 2-chloroethanol are added dropwise at 4050 over 15minutes. The reaction is then refluxed with stirring for 1 hour, cooledto room temperature and the solid removed by filtration. The solvent isremoved from the filtrate under reduced pressure and 33.4 parts ofthiourea and parts of concentrated hydrochloric acid are added. Thereaction is refluxed with stirring under nitrogen for 2 /2 hours andparts by volume of water, dried over magnesium sulfate and evaporated.The residue is vacuum distilled to yield the desiredn-dodecylthioethylmercaptan, B.P. 119121/ 0.010 mm.

Calc. for C H S C, 64.06; H, 11.52; S, 24.43. Found: C, 64.07; H, 11.61;S, 24.15.

(b) 6-(4-hydr0xy-3,5-di-t-bulylphenoxy)-2,4bis-(ndodecylthioethylzhio)-1,3,5-triazine.-A solution L 9.2 parts ofcyanuric chloride and 26.2 parts of n-dodecylthioethylmercaptan in 100parts by volume of acetone is stirred under nitrogen at 8 while 8.0parts of 50% sodium hydroxide are added dropwise over 30 minutes.2,6-di-t-butylhydroquinone (11.1 parts) are then added and the reactionstirred at 12 while adding 4.0 parts of 50% sodium hydroxide dropwiseover 15 minutes. Stirring is continued for 1 hour without cooling afterwhich, the PH is adjusted to 5.5 with concentrated hydrochloric acid.The solvent is removed under reduced pressure, the residual oil boiledwith 300 parts by volume of ethanol, the salt filtered and the filtrateallowed to cool slowly, adding a few drops of ethyl acetate to preventoiling. The product thus formed is cooled, collected by filtration,washed with cold ethanol, air dried and recrystallized twice fromethanol to yield6-(4-hydroxy-3,S-di-t-butylphenoxy)-2,4-bis-(n-dodecylthioethylthio)1,3,5 triazine, M.P. 44-46 thiopropylthio)-1,3,5-triazine may besimilarly prepared as follows:

A solution of 9.2 parts of cyanuric chloride and 220 parts ofn-octylthiopropylmercaptan (prepared as in Example 21) in 200 parts byvolume of acetone are stirred under a nitrogen atmosphere at 05 while8.0 parts of 50% sodium hydroxide are added dropwise over 25 minutes.Stirring is continued for 30 minutes at 5 and 11.1 parts of2,6-d-i-tbutylhydroquinone are added, followed by an additional 4.0parts of 50% sodium hydroxide dropwise over 15 minutes at 510. Thereaction is stirred for 1 hour at the pH adjusted to 5 with concentratedhydrochloric acid and allowed to stand overnight at room temperature.The solvent is then removed under reduced pressure, the residual oildissolved in 150 parts by volume of hexane and filtered to remove thesalt and the hexane evaporated under reduced pressure. The last tracesof solvent are removed at 100/100 mm. and the product filtered to removea small amount of turbidity. There is thus obtained6-(4-hydroxy-3,S-di-t-butylphenoxy)-4,6- bis- (n-octylthiopropylthio 1,3,5 -triazine.

Calc. for C H O N S S, 17.38. Found: S, 17.20.

EXAMPLE 21 2,4-bis- (4-hydroxy-3,5-di-t-butylphen0xy -6- (nroclythiopropy l till 0 -1 ,3,5 -friazine (a) n-Octylrhi0propylchloride.Asolution of 157.45 parts of 1-chloro-3-bromopropane in 200 parts byvolume of ethanol is stirred under nitrogen while adding a solution of150.2 parts of 97% n-octylmercaptan and 54.03 parts of sodium methylatein 250 parts by volume of ethanol over 30 minutes, keeping thetemperature below 50. The reaction mixture is then refluxed for 1 hour18 and the solvent removed under reduced pressure. The residue isdistilled at 8486/0.005 mm. to yield n-octyl thiopropyl chloride, n1.475O.

Calc. for C H SCl: C, 59.25; H, 10.4; Cl, 15.92. Found: C, 59.15; H,10.19; Cl, 16.01.

(b) n-Octylthi0pr0pylmercaptan.A solution of 111.4 parts ofn-octylthiopropyl chloride and 38.0 parts of thiourea in parts by volumeof Cel-losolve is refluxed for 3 hours, allowed to cool to roomtemperature, diluted with 300 parts by volume of water containing 40parts of 50% sodium hydroxide and refluxed for an additional 3 hours.After cooling to room temperature, an additional 300 parts by volume ofwater are added and the oil extracted with 500 parts by volume of ether.These extracts are washed two times with 250 parts of water and driedover magnesium sulfate. The ether is removed under reduced pressure andthe product distilled at 84/ 0.010 mm. n 1.4926.

Calc. for C H S c, 59.24; H, 10.97; s, 29.10. Found: C, 60.29; H, 10.69;S, 28.54.

By employing an equivalent amount of 1-chloro-6- bromohexane in theprocedure of part (a) of this example and thereafter executing theprocedure of part (b), there is obtained n-octylthiohexylmercaptan.

(c) 2,4-bis-(4-hydr0xy-3,5-di-f-butylplzenoxy) 6 (noctylthiopropylthio)-1,3,5-trfaZine.A solution of 9.2 parts of cyanuricchloride and 11.0 parts of n-octylthiopropylrnercaptan in 200 parts byvolume of acetone is stirred under nitrogen at 0-5 while 4.0 parts of50% sodium hydroxide are added dropwise over 30 minutes. 2,6-di-tbutylhydroquinone (22.2 parts) is then added and stirring is continuedat 10 while 8.0 parts of 50% sodium hydroxide are added over 30 minutes.Stirring is continued for an additional hour at 10, the pH adjusted to 5.5 with concentrated hydrochloric acid and the solvent removed underreduced pressure. The residue is dissolved in parts by volume of boilingisopropyl alcohol and filtered to remove the salt, after which 15 partsby volume of water are added. Upon cooling, the product crystallizes andthis is collected by filtration, washed with 100 parts by volume of 75%isopropyl alcohol, air dried and recrystallized several times frompetroleum ether to yield 2,4bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-(n-octylthiopropylthio)-1,3,5-triazine.

Calc. for C H O N S C, 68.16; H, 8.85; N, 5.68; S, 8.67. Found: C,68.14; H, 8.87; N, 5.60; S, 8.70.

In a similar fashion,2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-(n-octylthiohexylthio)-1,3,5-triazineis obtained by substituting an equivalent amount ofn-octylthiohexylmercaptan for n-octylthiopropylmercaptan in thisprocedure.

Likewise by employing an equivalent amount ofndodecylthioethylmercaptan, there is obtained 2,4-bis-(4- hydroxy 3,5di-t-butylphenoxy)-6- (n-dodecylthioethylthio)-1,3,5-triazine, whichafter recrystallization from isopropyl alcohol demonstrates a meltingpoint of 91-93".

Similarly the use of n-octylthioethylmercaptan in equivalent amountsyields 2,4-bis-(4-hydroxy-3,5di-t?butylphenoxy)-6-(n-octylthioethylthio) 1,3,5 triaziue, which afterrecrystallization from ethanol/water demonstrates a melting point of94-95 By substituting 88 parts of n-octylthioethylmercaptan forn-dodecylmercaptan in the procedure of part (a) of Example 20, there isobtained n-octylthioethylthioethylmercaptan which when resubjected tothe identical procedure in equivalent amounts yieldsn-octylthioethylthioethylthioethylmercaptan. Substitution of this lattercompound in the procedure of part (c) of this example then yields2,4-bis- 4-hydroxy-3 ,5 -di-t-butylphenoxy -6-(n-octylthio-ethylthioethylthioethylthio)-1,3,54triazine whilesubstitution of the former yields2,4-bis-(4ahydroxy-3,5-di-tbutylphenoxy) 6(n-octylthioethylthioethylthio)-1,3,5- triazine, M.P. 94-97.

1 9 EXAMPLE 222,4-bis-(4-hydr0xy-3,S-di-t-butylphenoxy)-6-(n-d0decylamino)-1,3,5-triazine A solution of 11.12 parts of2,4-bis-(4-hydroxy-3,5-dit-butylphenoxy)-6-chloro-1,3,5-triazine and 3.7parts of n-dodecylamine in 100 parts by volume of acetone is stirreduntil the exothermic reaction has subsided and 3.8 parts by volume of5.29 N sodium hydroxide are added dropwise with stirring over minutes.Stirring is continued for 2 hours after which 40 parts by volume ofwater are added. The solid product is collected by filtration, washedwith water, air dried and sequentially recrystallized from ethanol,heptane and hexane/ethyl acetate to yield the product, M.P. 177180.

Calc. for C H O N C, 73.24; H, 9.72; N, 7.95. Found: C, 73.16; H, 9.71;N, 7.95.

By employing equivalent amounts of dimethylamine, di-(2-ethy1hexyl)amineand dibutylamine in the above procedure there are respectively obtained,2,4-bis-(4- hydroxy 3,5 di t butylphenoxy) 6 dimethylamino-1,3,5-triazine, M.P. 244246; 2,4-bis-(4-hydroxy-3,5-di-tbutylphenoxy) 6(diQ-ethylhexylamino)-1,3,5-triazine, M.P. 130-132; and2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-dibutylamino-l,3,5-triazine,M.P. 193194.

In a similar fashion, by passing anhydrous ammonia through an anhydroussolution of 2,4-bis-(4-hydroxy-3,5-di-t-butylphenoxy)-6-chloro-1,3,5-triazine, there is obtained2,4-bis-(4-hydroxy-3,5 di t butylyphenoxy)-6- amino-1,3,5-triazine whichafter recrystallization from benzene melts at 289291.

EXAMPLE 23 Unstabilized polypropylene powder (Hercules Profax 6501) isthoroughly blended with 0.5% by weight of the following compounds ofthis invention and milled on a two-roller mill at 182 for minutes, afterwhich time the stabilized polypropylene is sheeted from the mill andallowed to cool.

The milled polypropylene sheet is cut into small pieces and pressed forfrom 510 minutes on a hydraulic press at 218 and 175 pounds per squareinch pressure. The resultant sheet of 25 mil thickness is then testedfor resistance to accelerated aging in a forced draft oven at 149. Theunstabilized polypropylene deteriorates after 3 hours. The followingtable presents representative oven lives for polypropylene stabilized byvarious compounds of the present invention.

Compound: Hours to failure 6- (4-hydr0xy-3-methyl-5-t-butylanilino -2,4-bis- (n-octylthio)-1,3,5-triazine 515 6- (4-hydroxyanilino -2,4-bis-(n-octylthio -1 ,3 ,5

triazine 340 6- (4-hydr0xy-3 ,5 -dimethylanilino -2,4-bis-(n-octylthio)-1,3,5-triazine 515 6- 4-hydroxy-3 ,S-di-t-butylanilino)-2,4-bis- (n-octylthioethylthio l ,3 ,5 -triazine 705 6-(4-l1ydroxyphenoxy -2,4-bisn-octylthio 1,3,5-triazine 750 2,4-bis-(4-hydroxy-3 ,5 -di-t-butylphenoxy -6- (n-octylthio)-l,3,5-triazine 8052,4-bis- (4-hydroxy-3-t-butylphenoxy) -6- (noctylthio)-1,3,5-triazine940 6- 4-hydr0xy-3 ,5 di-t-butylanilino -2,4-bis-(phenoxy)-1,3,5-triazine 380 6- (4-hydr0xy-3 ,S-di-t-butylanilino -4-4-hydroxy- 3 ,5-di-t-butylphenoxy)-2-(n-octylthio) -1,3,5- triazine 6102,4,6-tris- (4-hydroxy-3 ,5 -di-t-buty1- phenoxy)-l,3,5-triazine 180 6-(4-hydroxy-3 ,5 -di-t-butylpl1enoxy) -2,4-bis- (n-octylthioethylthio)-1,3,5-triazine 1600 6- 4-hydroxy-3,5-di-t-butylanilino -2,4-bis-(n-octylthio)-1,3,5-triazine 375 20 Compound-Continued Hours to failure6 (4-hydroxy-3 -methylphenoxy) -2,4-bis- (noctylthio) -1,3 ,S-triazine6- 4-hydroxy-3-t-butylphenoxy -2,4-bis- (n-o ctylthioethylthio)-1,3 ,5-triazine 1745 6- 4-hydroxy-3-methy1-5-t-butylphenoxy) -2,4-

bis-(n-octylthio -1,3,5-triazine 2,4bis(4-hydroxy-3-methyI-S-t-butyl-phenoxy 6-(n-octylthio)-1,3,5-triazine1530 2,4,6-tris- (4-hydr-oxy-3 -methyl-5-t-butylphenoXy)-1,3,5-triazine45 2,4-bis- (4-hydroxy-3 ,5 -di-t-butylphenoxy -6- amino-1,3,5-triazine655 2,4-bis- (4-hydroxy-3 ,5 -di-t-butylphenoxy) -6- dimethylamino-1,3,5 -triazine 620 2,4-bis- (4-hydroxy-3,5-di-t-butylphenoxy -6-dodecylamino-1,3,5-triazine 715 2,4-bis- (4-hydroxy-3,S-di-t-butylphenoxy) -6- (di-2-ethylhexyl) amino-1,3 ,5 -triazine 7302,4-bis- (4-hydroxy-3,5-di-t-butylphenoxy -6- dibutylamino-1,3 ,5-triazine 5 2.4-bis- (4-hydroxy-3,S-di-t-butylanilino -6- (n-octylthio)1,3,5-triazine 300 6-(4-hydroxy-3 ,5 -di-t-butylphenoxy) 2,4 bis-(noctylthiopropylthio)-1,3,5-triazine 20 10 6-(4-hydroxy-3,5-di-t-butylphenoxy) 2,4-bis- (ndo decylthioethylthio 1,3,5-triazine 1570 2,4-bis-(4-hydroxy-3 ,5 di-t-4b-utylphenoxy)-6-butylthio-1,3,5-triazine 695 2,4-bis- (4-hydroxy-3 ,5di-t-butylphenoxy -6- (noctadecylthio 1,3,5 -triazine 1500 2,4bis-(4-hydroxy-3,5 di-t-butylphenoxy) -6 (ndo decylthio 1,3,5 -triazine 8932,4- bis- (4-hydroxy-3,5 di-t-butylphenoxy) -6-(noctylth-iopropylthio)-1,3,5-triazine 1465 2,4-bis- (4-hydroxy-3 ,5di-t-butylphenoxy) -6- (noctylthioethylthio)-1,3 ,5 -triazine 8 252,4-bis-(4-hydroxy-3,5di-t-butylphenoxy)-6-(ndodecylthioethylthio)-1,3,5-triazine 1450Similarly compositions of polyethylene, polystyrene and the like arehighly stabilized by the compounds of this invention.

EXAMPLE 24 A stalbilized mineral oil composition is prepared byincorporating 0.005% by weight of total compositions of the stabilizer6-(4=hydroxy-3,5-di-t-butylanilino)-2,4-bis (n-octylthio)-1,3,5-triazinein white mineral oil, U.S.P. The mixture is heated for 5 hours at 115 inthe presence of air. A similar amount of unstalbilized mineral oil isalso heated for 5 hours at 115. The stabilized mineral oil is odorless,while the unstabilized mineral oil exhibits a strong odor.

EXAMPLE 25 A stabilized gasoline is prepared by incorporating into Texascracked gasoline having no additives therein, 0.05% by Weight of6-(4-hydroxy-3,5-di-Fbutylanilino)-2,4-bis-(n-octylthio)-1,3,5-triazine. The gasoline is tested by the oxygen bombinduction period method (ASTM D525-55). Gasoline containing stabilizerfails after 65 hours, whereas the blank fails after 4 hours.

EXAMPLE 2-6 Stabilized lard is prepared by incorporating in lard 0.01%by Weight of 6-(4-hydroxy-3,S-di-t butylanilino)- 2,4 bis (n-octylthio)1,3,5 triazine. Air is bubbled through both the stabilized and theUnstabilized lard for 25.5 hours at The peroxide value of the stabilizedlard after this aeration is 28, while the unstabilized lard has aperoxide value of 55-6.

EXAMPLE 27 A stabilized high temperature lubricating oil is prepared bymcorporating 2% by Weight of 6-(4-hydroxy- 3,5-d1-t-butylan1lino)2,4 bisa (n-octylthio)l,3,5-triazine EXAMPLE 28 Heptaldehyde is stabilized byincorporating into the freshly dis-tilled aldehyde 0.01% by weight of6-(4-hydroxy-S,5-di-t butylanilino)-2,4-bis (n-octylthio) 1,3,5-triazine. The stabilized kept-aldehyde is shaken in an oxygen atmosphereunder normal pressure at room temperature (23). The time necessary forabsorption of 30 parts by volume of oxygen in 25 parts of heptaldehydeis 11 hours for the stabilized heptaldehyde, compared with minutes forheptaldehyde alone.

EXAMPLE 29 Cyclohexene, freshly distilled, is stabilized by additionthereto of 0.001% by weight 6-(4-hydroxy-3,S-di-t-butyllanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine. The effectiveness of this stabilizerin cyclohexene is tested by the ASTM D525-55 oxidation test with themodification that only 10 parts by volume of cyclohexene are used ineach bomb. The stabilized cyclohexene runs 90 minutes to failure, whileunstabilized cyclohexene fails after 35 min utes.

EXAMPLE 3O Paraffin wax is stabilized by incorporating therein 0.001% byweight of 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-(n-octylthio)-l,3,5-triazine. The effective stabilization isevidenced by odor formation. After hours there is no perceptible odorfor the stabilized wax whereas unstabilized wax exhibits a distinctodor.

EXAMPLE 31 6-(4-hydroxy-3,5 di-t-butylphenoxy) 2,4 dichloro-1,3,5-triazine, prepared according to Example 19, is treated withstoichiometrically equivalent amounts of appropriately-substitutedphenols by the procedure of Example l7 and the following additionalstabilizers are prepared:

6- (4-hydroxy-3 ,5 di-t-butylphenoxy) -2,4-bis- (4- methylphenoxy)-1,3,5-triazine,

6- (4-hydroxy-3,5-di-t-butylphenoxy -2,4-bis- (4- bis-(4-t-butylphenoxy)-1,3 ,5 triazine,

6- (4-hydroxy-3 ,5 di-t-butylphenoxy) -2,4-bis 4- octylphenoxy)-1,3,S-triazine,

6- (4-hydroxy-3,S-di-t-butylphenoxy) -2,4-bis- (4-dodecylphenoxy)-1,3,5-triazine,

6- (4-hydroxy-3,S-di-t-butylphenoxy -2,4-bis- 2,4-didodecylphenoxy)1,3,5 triazine.

In a similar manner2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-chloro-1,3,5-triazine isreacted with the appropriate phenols and there are obtained thefollowing stabilizers:

2,4-bis- (4-hydroxy-3 ,5 di-t-butylphenoxy) 6- phenoxy) l ,3,5-triazine,

2,4-bis- (4-hydroxy-3,S-di-t-butylphenoxy) 6- (4- rnethylphenoxy) -1,3,5 triazine,

2,4-bis- (4-hydroxy-3 ,5 di-t-butylphenoxy) -6- (4-t-butylphenoxy) -1,3,5 triazine,

2,4-bis- (4-hydroxy-3,S-di-t-butylphenoxy) -6- (4-octylphenoxy) -1,3,5-triazine,

2,4-bis- (4-hydroxy-3,5-di-t-butylphenoxy) -6- (4-t-dodecylphenoxy)-1,3,5-triazine,

2,4-bis- 4-hydroxy-3,S-di-t-butylphenoxy) 6- (2,4-didodecylphenoxy)-1,3,5-triazine.

22 What is claimed is: 1. Compounds of the formula:

wherein R and R are each and each of X and Y is selected from the groupconsisting of O-, S and II I (CnH2a) H in which each of n, m, z and yhas a value of from 0 to 12 and a has a value of from 0 to 30. 2.Compounds of the formula:

wherein R and R are each and each of X and Y is selected from the groupconsisting of -O, S and J m-H in which each of n, m, z and y has a valueof from 0 to 12,

and a has a value of from 0 to 30. 3. Compounds of the formula:

23 24 and each of X and Y is selected from the group consistingReferences Cited by the Examiner of and UNITED STATES PATENTS 2,387,54710/1945 Widmer et al. 260249.5 X (CnHm-H 5 2,481,155 9/1949 Schaefer260-2495 X in which each of n, m, z and y has a value of from 0 to 12,

and a has 12. value of firorn O to '30, WALTER A. MODANCE, PrimaryExaminer.

4. 6 (4 hydroxy-3,5di-t-butylanilino)-2,4-bis-(phe- JOHN D. RANDOLPH, I.M. FORD, noxy)-1,3,5-triazine. Assistant Examiners.

1. COMPOUNDS OF THE FORMULA: